Variation in the Bandgap of Amorphous Zinc Tin Oxide: Investigating the Thickness Dependence via In Situ STS.

Amorphous transparent conducting oxides (a-TCOs) have seen substantial interest in recent years due to the significant benefits that they can bring to transparent electronic devices. One such material of promise is amorphous ZnxSn1-xOy (a-ZTO). a-ZTO possesses many attractive properties for a TCO such as high transparency in the visible range, tunable charge carrier concentration, electron mobility, and only being composed of common and abundant elements. In this work, we employ a combination of UV-vis spectrophotometry, X-ray photoemission spectroscopy, and in situ scanning tunneling spectroscopy to investigate a 0.33 eV blue shift in the optical bandgap of a-ZTO, which we conclude to be due to quantum confinement effects.

Miniaturized spectrometer with intrinsic long-term image memory.

Miniaturized spectrometers have great potential for use in portable optoelectronics and wearable sensors. However, current strategies for miniaturization rely on von Neumann architectures, which separate the spectral sensing, storage, and processing modules spatially, resulting in high energy consumption and limited processing speeds due to the storage-wall problem. Here, we present a miniaturized spectrometer that utilizes a single SnS2/ReSe2 van der Waals heterostructure, providing photodetection, spectrum reconstruction, spectral imaging, long-term image memory, and signal processing capabilities. Interface trap states are found to induce a gate-tunable and wavelength-dependent photogating effect and a non-volatile optoelectronic memory effect. Our approach achieves a footprint of 19 µm, a bandwidth from 400 to 800 nm, a spectral resolution of 5 nm, and a > 104 s long-term image memory. Our single-detector computational spectrometer represents a path beyond von Neumann architectures.

The topological soliton in Peierls semimetal Sb.

Sb is a three-dimensional Peierls insulator. The Peierls instability gives rise to doubling of the translational period along the [111] direction and alternating van der Waals and covalent bonding between (111) atomic planes. At the (111) surface of Sb, the Peierls condition is violated, which in theory can give rise to properties differing from the bulk. The atomic and electronic structure of the (111) surface of Sb have been simulated by density functional theory calculations. We have considered the two possible (111) surfaces, containing van der Waals dangling bonds or containing covalent dangling bonds. In the models, the surfaces are infinite and the structure is defect free. Structural optimization of the model containing covalent dangling bonds results in strong deformation, which is well described by a topological soliton within the Su-Schrieffer-Heeger model centered about 25 Å below the surface. The electronic states associated with the soliton see an increase in the density of states (DOS) at the Fermi level by around an order of magnitude at the soliton center. Scanning tunneling microscopy and spectroscopy (STM/STS) measurements reveal two distinct surface regions, indicating that there are different surface regions cleaving van der Waals and covalent bonds. The DFT is in good agreement with the STM/STS experiments.

Effect of Rapid Thermal Annealing on Si-Based Dielectric Films Grown by ICP-CVD.

Silicon nitride, silicon oxide, and silicon oxynitride thin films were deposited on the Si substrate by inductively coupled plasma chemical vapor deposition and annealed at 1100 °C for 3 min in an Ar environment. Silicon nitride and silicon oxide films deposited at ratios of the reactant flow rates of SiH4/N2 = 1.875 and SiH4/N2O = 3, respectively, were Si-rich, while Si excess for the oxynitride film (SiH4/N2/N2O = 3:2:2) was not found. Annealing resulted in a thickness decrease and structural transformation for SiOx and SiNx films. Nanocrystalline phases of Si as well as α- and ß-Si3N4 were found in the annealed silicon nitride film. Compared to oxide and nitride films, the oxynitride film is the least susceptible to change during annealing. The relationship between the structure, composition, and optical properties of the Si-based films has been revealed. It has been shown that the calculated optical parameters (refractive index, extinction coefficient) reflect structural peculiarities of the as-deposited and annealed films.

Nitrate removal in iron sulfide-driven autotrophic denitrification biofilter: Biochemical and chemical transformation pathways and its underlying microbial mechanism.

Iron sulfides-based autotrophic denitrification (IAD) is effective for treating nitrate-contaminated wastewater. However, the complex nitrate transformation pathways coupled with sulfur and iron cycles in IADs are still unclear. In this study, two columns (abiotic vs biotic) with iron sulfides (FeS) as the packing materials were constructed and operated continuously. In the abiotic column, FeS chemically reduced nitrate to ammonium under the ambient condition; this chemical reduction reaction pathway was spontaneous and has been overlooked in IAD reactors. In the biotic column (IAD biofilter), the complex nitrogen-transformation network was composed of chemical reduction, autotrophic denitrification, dissimilatory nitrate reduction to ammonium (DNRA) and sulfate reducing ammonium oxidation (Sulfammox). Metagenomic analysis and XPS characterization of the IAD biofilter further validated the roles of functional microbial communities (e.g., Acidovorax, Diaphorobacter, Desulfuromonas) in nitrate reduction process coupled with iron and sulfur cycles. This study gives an in-depth insight into the nitrogen transformations in IAD system and provides fundamental evidence about the underlying microbial mechanism for its further application in biological nitrogen removal.

Terbium-doped carbon dots (Tb-CDs) as a novel contrast agent for efficient X-ray attenuation.

Metal-doped carbon dots have attracted considerable attention in nanomedicine over the last decade owing to their high biocompatibility and great potential for bioimaging, photothermal therapy, and photodynamic therapy. In this study, we prepared, and for the first time, examined terbium-doped CDs (Tb-CDs) as a novel contrast agent for computed tomography. A detailed physicochemical analysis revealed that the prepared Tb-CDs have small sizes (∼2-3 nm), contain relatively high terbium concentration (∼13.3 wt%), and exhibit excellent aqueous colloidal stability. Furthermore, preliminary cell viability and CT measurements suggested that Tb-CDs exhibit negligible cytotoxicity toward L-929 cells and demonstrate high X-ray absorption performance (∼48.2 ± 3.9 HU L g-1). Based on these findings, the prepared Tb-CDs could serve as a promising contrast agent for efficient X-ray attenuation.

High-rate iron sulfide and sulfur-coupled autotrophic denitrification system: Nutrients removal performance and microbial characterization.

Iron sulfides-based autotrophic denitrification (IAD) is a promising technology for nitrate and phosphate removal from low C:N ratio wastewater due to its cost-effectiveness and low sludge production. However, the slow kinetics of IAD, compared to other sulfur-based autotrophic denitrification (SAD) processes, limits its engineering application. This study constructed a co-electron-donor (FeS and S0 with a volume ratio of 2:1) iron sulfur autotrophic denitrification (ISAD) biofilter and operated at as short as 1 hr hydraulic retention time (HRT). Long-term operation results showed that the superior total nitrogen and phosphate removals of the ISAD biofilter were 90-100% at 1-12 h HRT, with the highest denitrification rate up to 960 mg/L/d. Considering low sulfate production, HRT of 3 h could be the optimal condition. Such superior performance in the ISAD biofilter was achieved due to the interactions between FeS and S0, which accelerated the denitrification process and maintained the acidity-alkalinity balance. Metagenomic analysis found that the enriched nitrate-dependent iron-oxidizing (NDFO) bacteria (Acinetobacter and Acidovorax), sulfur-oxidizing bacteria (SOB), and dissimilatory nitrate reduction to ammonia (DNRA) bacteria likely supported stable nitrate reduction. The metabolic pathway analysis showed that completely denitrification and DNRA, coupled with sulfur oxidation, disproportionation, iron oxidation and phosphate precipitation with FeS and S0 as co-electron donors, were responsible for the high-rate nitrate and phosphate removal. This study provides the potential of ISAD as a highly efficient post-denitrification technology and sheds light on the balanced microbial S-N-Fe transformation.

VOx Phase Mixture of Reduced Single Crystalline V2O5: VO2 Resistive Switching.

The strongly correlated electron material, vanadium dioxide (VO2), has seen considerable attention and research application in metal-oxide electronics due to its metal-to-insulator transition close to room temperature. Vacuum annealing a V2O5(010) single crystal results in Wadsley phases (VnO2n+1, n > 1) and VO2. The resistance changes by a factor of 20 at 342 K, corresponding to the metal-to-insulator phase transition of VO2. Macroscopic voltage-current measurements with a probe separation on the millimetre scale result in Joule heating-induced resistive switching at extremely low voltages of under a volt. This can reduce the hysteresis and facilitate low temperature operation of VO2 devices, of potential benefit for switching speed and device stability. This is correlated to the low resistance of the system at temperatures below the transition. High-resolution transmission electron microscopy measurements reveal a complex structural relationship between V2O5, VO2 and V6O13 crystallites. Percolation paths incorporating both VO2 and metallic V6O13 are revealed, which can reduce the resistance below the transition and result in exceptionally low voltage resistive switching.

4D printing of MXene hydrogels for high-efficiency pseudocapacitive energy storage.

2D material hydrogels have recently sparked tremendous interest owing to their potential in diverse applications. However, research on the emerging 2D MXene hydrogels is still in its infancy. Herein, we show a universal 4D printing technology for manufacturing MXene hydrogels with customizable geometries, which suits a family of MXenes such as Nb2CTx, Ti3C2Tx, and Mo2Ti2C3Tx. The obtained MXene hydrogels offer 3D porous architectures, large specific surface areas, high electrical conductivities, and satisfying mechanical properties. Consequently, ultrahigh capacitance (3.32 F cm-2 (10 mV s-1) and 233 F g-1 (10 V s-1)) and mass loading/thickness-independent rate capabilities are achieved. The further 4D-printed Ti3C2Tx hydrogel micro-supercapacitors showcase great low-temperature tolerance (down to -20 °C) and deliver high energy and power densities up to 93 µWh cm-2 and 7 mW cm-2, respectively, surpassing most state-of-the-art devices. This work brings new insights into MXene hydrogel manufacturing and expands the range of their potential applications.

Role of iron(II) sulfide in autotrophic denitrification under tetracycline stress: Substrate and detoxification effect.

Autotrophic denitrification using inorganic compounds as electron donors has gained increasing attention in the field of wastewater treatment due to its numerous advantages, such as no need for exogenous organic carbon, low energy input, and low sludge production. Tetracycline (TC), a refractory contaminant, is often found coexisting with nutrients (NO3- and PO43-) in wastewater, which can negatively affect the biological nutrient removal process because of its biological toxicity. However, the performance of autotrophic denitrification under TC stress has rarely been reported. In this study, the effects of TC on autotrophic denitrification with thiosulfate (Na2S2O3) and iron (II) sulfide (FeS) as the electron donors were investigated. With Na2S2O3 as the electron donor, TC slowed down the nitrate removal rate, which decreased from 1.32 to 0.18 d-1, when TC concentration increased from 0 mg/L to 50 mg/L. When TC concentration was higher than 2 mg/L, nitrite reduction was seriously inhibited, leading to nitrite accumulation. With FeS as the electron donor, nitrate removal was much more efficient under TC-stressed conditions, and no distinct nitrite accumulation was observed when the initial TC concentration was as high as 10 mg/L, indicating the effective detoxification of FeS. The detoxification effects in the FeS autotrophic denitrification system mainly resulted from the rapid adsorption of TC by FeS and effective degradation of TC, as proven by a relatively higher living biomass area. This study offers new insights into the response of sulfur-based autotrophic denitrifiers to TC stress and demonstrates that the FeS-based autotrophic denitrification process is a promising technology for the treatment of wastewater containing emerging contaminants and nutrients.

An In Situ Study of Precursor Decomposition via Refractive Index Sensing in p-Type Transparent Copper Chromium Oxide.

Oxide semiconductors are penetrating into a wide range of energy, environmental, and electronic applications, possessing a potential to outrun currently employed semiconductors. However, an insufficient development of p-type oxides is a major obstacle against complete oxide electronics. Quite often oxide deposition is performed by the spray pyrolysis method, inexpensive to implement and therefore accessible to a large number of laboratories. Although, the complex growth chemistry and a lack of in situ monitoring during the synthesis process can complicate the growth optimization of multicomponent oxides. Here we present a concept of plasmonic, optical sensing that has been applied to spray pyrolysis oxide film growth monitoring for the first time. The proposed method utilizes a polarization based refractive index sensing platform using Au nanodimers as transducing elements. As a proof of concept, the changes in the refractive index of the grown film were extracted from individual Cu(acac)2 and Cr(acac)3 precursors in real time to reveal their thermal decomposition processes. Obtained activation energies give insight into the physical origin of the narrow temperature window for the synthesis of high performing p-type transparent conducting copper chromium oxide Cu x CrO2. The versatility of the proposed method makes it effective in the growth rate monitoring of various oxides, exploring new candidate materials and optimizing the synthesis conditions for acquisition of high performing oxides synthesized by a high throughput cost-effective method.

The influence of drinking water constituents on the level of microplastic release from plastic kettles.

Microplastic (MP) release from household plastic products has become a global concern due to the high recorded levels of microplastic and the direct risk of human exposure. However, the most widely used MP measurement protocol, which involves the use of deionized (DI) water, fails to account for the ions and particles present in real drinking water. In this paper, the influence of typical ions (Ca2+/HCO3-, Fe3+, Cu2+) and particles (Fe2O3 particles) on MP release was systematically investigated by conducting a 100-day study using plastic kettles. Surprisingly, after 40 days, all ions resulted in a greater than 89.0% reduction in MP release while Fe2O3 particles showed no significant effect compared to the DI water control. The MP reduction efficiency ranking is Fe3+ ≈ Cu2+ > Ca2+/HCO3- > > Fe2O3 particles ≈ DI water. Physical and chemical characterization using SEM-EDX, AFM, XPS and Raman spectroscopy confirmed Ca2+/HCO3-, Cu2+ and Fe3+ ions are transformed into passivating films of CaCO3, CuO, and Fe2O3, respectively, which are barriers to MP release. In contrast, there was no film formed when the plastic was exposed to Fe2O3 particles. Studies also confirmed that films with different chemical compositions form naturally in kettles during real life due to the different ions present in local regional water supplies. All films identified in this study can substantially reduce the levels of MP release while withstanding the repeated adverse conditions associated with daily use. This study underscores the potential for regional variations in human MP exposure due to the substantial impact water constituents have on the formation of passivating film formation and the subsequent release of MPs.

Surface Modification and Subsequent Fermi Density Enhancement of Bi(111).

Defects introduced to the surface of Bi(111) break the translational symmetry and modify the surface states locally. We present a theoretical and experimental study of the 2D defects on the surface of Bi(111) and the states that they induce. Bi crystals cleaved in ultrahigh vacuum (UHV) at low temperature (110 K) and the resulting ion-etched surface are investigated by low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy (UPS), and scanning tunneling microscopy (STM) as well as spectroscopy (STS) techniques in combination with density functional theory (DFT) calculations. STS measurements of cleaved Bi(111) reveal that a commonly observed bilayer step edge has a lower density of states (DOS) around the Fermi level as compared to the atomic-flat terrace. Following ion bombardment, the Bi(111) surface reveals anomalous behavior at both 110 and 300 K: Surface periodicity is observed by LEED, and a significant increase in the number of bilayer step edges and energetically unfavorable monolayer steps is observed by STM. It is suggested that the newly exposed monolayer steps and the type A bilayer step edges result in an increase to the surface Fermi density as evidenced by UPS measurements and the Kohn-Sham DOS. These states appear to be thermodynamically stable under UHV conditions.

Atomic and Electronic Structure of a Multidomain GeTe Crystal.

Renewed interest in the ferroelectric semiconductor germanium telluride was recently triggered by the direct observation of a giant Rashba effect and a 30-year-old dream about a functional spin field-effect transistor. In this respect, all-electrical control of the spin texture in this material in combination with ferroelectric properties at the nanoscale would create advanced functionalities in spintronics and data information processing. Here, we investigate the atomic and electronic properties of GeTe bulk single crystals and their (111) surfaces. We succeeded in growing crystals possessing solely inversion domains of ∼10 nm thickness parallel to each other. Using HAADF-TEM we observe two types of domain boundaries, one of them being similar in structure to the van der Waals gap in layered materials. This structure is responsible for the formation of surface domains with preferential Te-termination (∼68%) as we determined using photoelectron diffraction and XPS. The lateral dimensions of the surface domains are in the range of ∼10-100 nm, and both Ge- and Te-terminations reveal no reconstruction. Using spin-ARPES we establish an intrinsic quantitative relationship between the spin polarization of pure bulk states and the relative contribution of different terminations, a result that is consistent with a reversal of the spin texture of the bulk Rashba bands for opposite configurations of the ferroelectric polarization within individual nanodomains. Our findings are important for potential applications of ferroelectric Rashba semiconductors in nonvolatile spintronic devices with advanced memory and computing capabilities at the nanoscale.

Low-Cost, High-Performance Spray Pyrolysis-Grown Amorphous Zinc Tin Oxide: The Challenge of a Complex Growth Process.

Transparent conductive oxides (TCOs) are important materials for a wide range of optoelectronic devices. Amorphous zinc tin oxide (a-ZTO) is a TCO and one of the best nontoxic, low-cost replacements for more expensive amorphous indium-gallium-zinc oxide. Here, we employ spray pyrolysis (SP), an inexpensive and versatile chemical vapor deposition-based technique, to synthesize a-ZTO with an as-deposited conductivity of ≈300 S/cm-the highest value hitherto among the reported solution-processed films. Compositional analysis via X-ray photoelectron spectroscopy reveals a nonstoichiometric transfer of Zn and Sn from the dissolved precursors into the film, with the best electrical properties achieved at a film composition of xfilm = 0.38 ± 0.04 ((ZnO)x(SnO2)1-x (0 < x < 1)). The morphology of these films is compared to films synthesized by physical vapor deposition (PVD), and a strong correlation between morphology and electrical properties is revealed. The granular nature of the SP-grown films, which seems like a drawback at first glance, brings about the prospect of using a-ZTO in ink-jet-printed films from a nanoparticle suspension for the room-temperature deposition. Brief post-anneal cycles in N2 gas improve the conductivity of the films by means of grain boundary (GB) passivation.

Deformation and fracture of crystalline tungsten and fabrication of composite STM probes.

Fracturing microscale constrictions in metallic wires, such as tungsten, platinum, or platinum-iridium, is a common fabrication method used to produce atomically sharp tips for scanning tunneling microscopy (STM), field-emission microscopy and field ion microscopy. Typically, a commercial polycrystalline drawn wire is locally thinned and then fractured by means of a dislocation slip inside the constriction. We examine a special case where a dislocation-free microscale constriction is created and fractured in a single crystal tungsten rod with a long side parallel to the [100] direction. In the absence of dislocations, vacancies become the main defects in the constriction which breaks under the tensile stress of approximately 10 GPa, which is close to the theoretical fracture strength for an ideal monocrystalline tungsten. We propose that the vacancies are removed early in the tensile test by means of deformation annealing, creating a defect-free tungsten constriction which cleaves along the W(100) plane. This approach enables fabrication of new composite STM probes which demonstrate excellent stability, atomic resolution and magnetic contrast that cannot be attained using conventional methods.

Low-temperature synthesis and electrocatalytic application of large-area PtTe2 thin films.

The synthesis of transition metal dichalcogenides (TMDs) has been a primary focus for 2D nanomaterial research over the last 10 years, however, only a small fraction of this research has been concentrated on transition metal ditellurides. In particular, nanoscale platinum ditelluride (PtTe2) has rarely been investigated, despite its potential applications in catalysis, photonics and spintronics. Of the reports published, the majority examine mechanically-exfoliated flakes from chemical vapor transport (CVT) grown crystals. This method produces high quality-crystals, ideal for fundamental studies. However, it is very resource intensive and difficult to scale up meaning there are significant obstacles to implementation in large-scale applications. In this report, the synthesis of thin films of PtTe2 through the reaction of solid-phase precursor films is described. This offers a production method for large-area, thickness-controlled PtTe2, potentially suitable for a number of applications. These polycrystalline PtTe2 films were grown at temperatures as low as 450 °C, significantly below the typical temperatures used in the CVT synthesis methods. Adjusting the growth parameters allowed the surface coverage and morphology of the films to be controlled. Analysis with scanning electron- and scanning tunneling microscopy indicated grain sizes of above 1 µm could be achieved, comparing favorably with typical values of ∼50 nm for polycrystalline films. To investigate their potential applicability, these films were examined as electrocatalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). The films showed promising catalytic behavior, however, the PtTe2 was found to undergo chemical transformation to a substoichiometric chalcogenide compound under ORR conditions. This study shows while PtTe2 is stable and highly useful for in HER, this property does not apply to ORR, which undergoes a fundamentally different mechanism. This study broadens our knowledge on the electrocatalysis of TMDs.

Solution-Based Deposition of Transparent Eu-Doped Titanium Oxide Thin Films for Potential Security Labeling and UV Screening.

Transparent titanium oxide thin films attract enormous attention from the scientific community because of their prominent properties, such as low-cost, chemical stability, and optical transparency in the visible region. In this study, we developed an easy and scalable solution-based process for the deposition of transparent TiOx thin films on glass substrates. We showed that the proposed method is also suitable for the fabrication of metal-doped TiOx thin films. As proof-of-the-concept, europium Eu(III) ions were introduced into TiOx film. A photoluminescence (PL) study revealed that Eu-doped TiOx thin films showed strong red luminescence associated with 5D0→7Fj relaxation transitions in Eu (III). We found that prepared TiOx thin films significantly reduce the transmittance of destructive UV radiation; a feature that can be useful for the protection of photovoltaic devices. In addition, transparent and luminescent TiOx thin films can be utilized for potential security labeling.

Tuning of oxygen vacancy-induced electrical conductivity in Ti-doped hematite films and its impact on photoelectrochemical water splitting.

Titanium (Ti)-doped hematite (α-Fe2O3) films were grown in oxygen-depleted condition by using the spray pyrolysis technique. The impact of post-deposition annealing in oxygen-rich condition on both the conductivity and water splitting efficiency was investigated. The X-ray diffraction pattern revealed that the films are of rhombohedral α-Fe2O3 structure and dominantly directed along (012). The as-grown films were found to be highly conductive with electrons as the majority charge carriers (n-type), a carrier concentration of 1.09×1020 cm-3, and a resistivity of 5.9×10-2 Ω-cm. The conductivity of the films were reduced upon post-deposition annealing. The origin of the conductivity was attributed firstly to Ti4+ substituting Fe3+ and secondly to the ionized oxygen vacancies (VO) in the crystal lattice of hematite. Upon annealing the samples in oxygen-rich condition, VO slowly depleted and the conductivity reduced. The photocurrent of the as-grown samples was found to be 3.4 mA/cm-2 at 1.23 V vs. RHE. The solar-to-hydrogen efficiency for the as-grown sample was calculated to be 4.18% at 1.23 V vs. RHE. The photocurrents were found to be significantly stable in aqueous environment. A linear relationship between conductivity and water-splitting efficiency was established.

Oxidation of Nb(110): atomic structure of the NbO layer and its influence on further oxidation.

NbO terminated Nb(110) and its oxidation are examined by scanning tunneling microscopy and spectroscopy (STS). The oxide structures are strongly influenced by the structural and electronic properties of the underlying NbO substrate. The NbO is terminated by one-dimensional few-nanometer nanocrystals, which form an ordered pattern. High-resolution STS measurements reveal that the nanocrystals and the regions between the nanocrystals exhibit different electronic characters. Low-dosage oxidation, sufficient for sub-monolayer coverage of the NbO, with subsequent UHV annealing results in the formation of resolved sub-nanometer clusters, positioned in-between the nanocrystals. Higher dosage oxidation results in the formation of a closed Nb2O5-y layer, which is confirmed by X-ray photoelectron spectroscopy measurements. The pentoxide is amorphous at the atomic-scale. However, large scale (tens of nanometers) structures are observed with their symmetry matching that of the underlying nanocrystals.